Effect of Surface Pt Doping on the Reactivity of Au(111) Surfaces towards Methanol Dehydrogenation: A First-Principles Density Functional Theory Investigation.

The surprisingly high catalytic activity of gold has been known to the heterogeneous catalysis community since the mid-1980s. Significant efforts have been directed towards improving the reactivity of these surfaces towards important industrial reactions. One such strategy is the introduction of small amounts of other metals to create Au-based surface alloys. In this work, we investigated the synergistic effect of the Pt doping of a Au(111) surface on decreasing the activation barrier of the methanol dehydrogenation elementary step within first-principles density functional theory. To this end, we constructed several models of Pt-doped Au(111) surfaces, including a full Pt overlayer and monolayer. The effect of Pt surface doping was then investigated via the computation of the adsorption energies of the various chemical species involved in the catalytic step and the estimation of the activation barriers of methanol dehydrogenation. Both the electronic and strain effects induced by Pt surface doping substantially lowered the activation energy barrier of this important elementary reaction step. Moreover, in the presence of preadsorbed atomic oxygen, Pt surface doping could be used to reduce the activation energy for methanol dehydrogenation to as low as 0.1 eV.